Process for treating a reaction mixture containing hydroxyalkyl cellulose and alkali



.tion degrades on standing is shown 2,698,254 Patented Dec. 28, 1954 ice PROCESS FOR TREATINGAREACTION "CONTAINING "HYDRDXYALKYL CELLULOSE AND ALKALI Harold "M;'Splirlin}Marshallton, Del.,- -assignor =to' 11ercules Powder-Company, wilmington, Del., a corporation ofDelaware No Drawing. Application March 30, 1951, Serial No.-. 218,533

2 Claims; (Cl; 106-497) fzThis invention relates, to a process for treating hydroxyalkyl cellulose, for example, hydroxyethyl: ,cellulose, containing. caustic-- alkali-to prevent-1: degradation duringwtorage andv conserve alkali ,values.

The reaction product of cellulose, alkali, water, and ethylene .oxide is essentially a mixture of hydroxyethyl cellulose, alkali, andwater. v Oxidative-degradation of the hydroxyethyl cellulose byjthe oxygen of the air is catalyzed by the alkali. Hydroxyethyl cellulose-from the reactor, if prepared from antordinary grade of linters or wood pulp, is, high in molecular Weight and too insoluble to be significant. utility. Degradation .of the reaction. mixture byexposure to .air can be effected very rapidly. For-example, U. S. 2,469,764 teaches, thatone .day s exposure at room temperature degradesa crude hydroxyethyl cellulose mixture to arangeusable inthe patent example. It .is therefore apparent that normal conditions of storage and transportation would allow an alkali-containing crude to.:degrade too far to 'be useful. Absolute exclusion of the oxygen of the air or theelimination ofthe alkaline catalyst rare the only preventives to chain breaking.

Now many uses of hydroxyethyl cellulose require its solvation. Exceptfor certain highly substituted and/or low molecular weight grades of hydroxyethyl cellulose, alkali is needed to eifect-solution or dispersion. Hence, conservation of the alkalibecomes a potent factor in the cost and hence the utility of the product.

:There .aretwo methods of handling the reaction-prodnot. known to the art. In the first, the reaction product vis diluted with water and, sufiicient alkali is added .to bring the resulting solution to the desired concentration.

Possible specificationfor'such asolution might-be 7-8% hydroxyethyl cellulose in 7%. alkali. Thatsuch a soluby its reduction in viscosity over a tWoor three-week period, although it is said to be stable when tightly stoppered and kept inthe dark. A serious economic objection'tothis approach is the necessity of shipping a product which-is 85%:water. ttlnnthet second method theareaction mixtureyis suspended in'70%- methanol (70. parts methanolto 30 parts water) and neutralized with acetic acid, the resulting free hydroxyethyl cellulose being washedfreeofzsalts and acid with successive portions of 70%, methanol, collected and dried. While'this dry product -is-indefinitely stable, the method wastes substantial quantities of alkali-because the substantial amounts originally present are lost and redisp'ersion by the customer in evenmore alkali than" was present inthe reaction mixture may berequired. -Moreoven-even in 70% methanol, a certain soluble portion of the hydroxyethyl cellulose is-lost.

lnqaccordance with this invention, a simpler rmore economical treatment of this reaction product or similar reaction products containing other hydroxyalkyl celluloses circumvents the objections to the above methods: namely, at least partial neutralization of the alkali present with carbon dioxile. Preferably, carbon dioxide is added until there is substantially no free alkali present. The mixture resulting from such a treatment comprises hydroxyethyl cellulose (or other hydroxyalkyl cellulose), water, sodium carbonate, and sodium bicarbonate. Becausethe free alkali content of the reaction product is at least spbstantially reduced, the hydroxyalkyl cellulose is much -less subject to oxidative chain breaking. Storage over reasonable periods and shipment are possible with -alkyl-- celluloseynamely, -=zbe-;understood,-however, that the. inventionwmay be used topreventundue degradation of any hydroxyalkylcellu- .lose, ebutyl noiunthenprocessing.except a possible evaporation of water toiproduce a dry mixture. It iseasily made ready for use by the addition of an appropriate metal oxide or hydroxide to react with the carbonate present and the addition of water and alkali'stifiicient to obtain solutions of the "desired concentration.

Having described the invention broadly, hereinafter the invention will be described in terms of a specific hydroxy- -hydroxyethylcellulose. It is to such as 2=hydroxypropyl cellulose and -2-hydroxycellulose,-:-;containing;. free .alkali. The following specific example will serve to point out how the broad principles of the invention-may be-utilized. -All parts and percentages are by weightvunlessotherwise indicated.

. EXAMPLE Following -thewteachings ofU. 8. 2,469,764,- asc'rudereaction" mixture wasprepared from 5 3 OpartsWoDdpuIp (6 moisture) 1,000.parts of 30% alkali 4.parts chlorine 11,001 parts ethylene .oxide 10 parts-of a 25% aqueous solution of the sodium salt of 2-thyl-hex-l-enesulfonic acid Chlorinewasadded as a .viscosity regulator-in 'place of the air degradation afterformation of .the hydroxyethyl .celluose.

. A 75-gramportion-of the reaction mixture was made up to 7.5 hydrox-yethyl cellulose and 7% sodium hydroxide in-watenand was designated Sample 1. This solution was allowed to stand one day. and the viscosity was measured. In two weeks the viscosity of the solution was measured again.

'Anotheruportion was removed from the reaction mix- .ture,-.suspended.in 70% methanol, acidified with acetic .acid to-the phenolphthalein endpoint and then washed with successive portions ofy-70% methanol until essentially ash free. It was designated Sample 2. Part of .this-lotwas used-for analytical determinations.

BY .analysisthe hydroxyethyl content was shown to be 12.8%,

"which isiequivalent to a degree of substitution of 0.378

hydroxyethyl group per anhydroglucose unit. The remainder of this sample notused 'for the analytical determinationswas stored for two weeks, then was made up -to 7 .5 hydroxyethyl cellulose and 7% sodium hydroxide in'water. The solution was allowed to stand one day and'the viscosity was-measured,

The pressure within the vessel containing the remainder of the reaction mixture was readjusted to 8 inches of mercury .(absolute) and the charge was agitated as carbon dioxide was-admitted to the bottle. After about 30 to .45. minutesyno further rapid a-bsorption was noted and tithe-bottle wastallowedto-stand 36 hours in an atmosphere toflcarbo'n dioxide.

' This material was designated Sample 3. Thefollowingtanalyticalidatatwereobtained for this sample:

* Percent .Hydroxyethyl -cellulose 29.0 Moi sture "Sample 3"Was s'tored'fortw'o weeksythen half was designated as 3A; and made up to 7.5%1hydroxyethyl cellulose and "7% :sodium' hydroxide in water by the 'addition'of water and sodium hydroxide. The other half of Sample 3 was designated 3B and was made up to 7.5% hydroxyethyl cellulose and 7% sodium hydroxide in water by adding water to the stored material, regenerating the original alkali values by adding lime, and then adding the additional requisite amount of sodium hydroxide. After standing for one day, the viscosity of both samples was measured to determine the degradation during the storage period.

The viscosities of all the samples appear in Table l. The period of one day before measurement was allowed to hydroxyethyl cellulose.

elapse so as to permit air entrapped in the solution during solvation to escape. on the spindle represented true solution viscosities. All viscosity determinations were made on solutions containing- 7.5% hydroxyethyl cellulose and 7% sodium hydroxide with a- Brookfield viscometer. A No. 4 spindle was used at 30 r. p. m.

Table 1 Sample Viscosity Crude 6, 300 Crude (in solution 2 weeks) 2, 600 Acldlfied, washed, and dried... 6, 300 C02 neutralized, then aged 2 week g,

alkali.

CO2 neutralized, aged, made up with lime and l All vlscositles, except the second, were measured on a solution l day d.

degradation without the necessity of excessive watering which would increase shipping costs and problems, and also eliminates the loss of hydroxyethyl cellulose and alkali values as well as the expense of washing with methanol which are attendant on the prior art acidification method.

The carbon dioxide treatment of the invention may be used to prevent oxidative degradation in the reaction mixtures of any of the known alkaline processes'for producing hydroxyethyl cellulose, for example, the dough process of U. S. 1,502,379 and the slurry process of U. S. 2,135,128 in addition to the dry alkaline process of U. S. 2,469,764. In the slurry process an inert organic medium will also be present, but this takes no part in the reactions and its presence is immaterial for the purposes of this invention. I

Any method of adding carbon dioxide may be used.

Thus, the carbon dioxide maybe bubbled through the reaction mixture, the reaction mixture may be stirred or tumbled in an atmosphere of carbon dioxide and the like. With respect to extent of neutralization, it is significant that the rate of degradation of the hydroxyethyl cellulose is a function of the concentration of the alkali. Where the hydroxyethyl cellulose is to be used within a relatively short time, it is possible to achieve sutficient stabilization thereof by using only the CO2 necessary to lower 'substantially the original alkali concentration of the crude Hence, -'-it, is within the broad scope of this invention to pass CO2-into a crude hydroxyethyl cellulose containing alkali to reduce substantially the free alkali content. It is preferred, however, in accordance with this invention, to pass in CO2 until there is substantially no free alkali present. While as normally operated it is sufficient to neutralize the crude hydroxyethyl cellulose only to the point that substantially no free alkali is present, it is sometimes desirable to carry the neutralization somewhat further. The most preferred procedure is to pass in CO2 until not only all the alkali has been neutralized but also a substantial amount of the alkali has been converted in the bicarbonate. The method of adding oxide or hydroxide to regenerate the alkali is imrnai 5 terial.

Thus, the viscosities of the solution Any metal oxide or hydroxide that will precipitate as the carbonate fro'rn'an aqueous alkali carbonate solution while regenerating caustic alkali may be used to regenerate the alkali. While any compound that is in this class is technically operable, lime is. preferred. Other suitable compounds are the oxides or hydroxides of barium and strontium. The factor of importance-here is that the hydroxide of the metal should have some slight solubility so that it can react in solution and that its carbonate have a low solubility relative to its hydroxide. It is to be noted that the color of the precipitated carbonates of the above n'ietals is white, which makes them desirable pigmenting agents for some uses of the hydroxyethyl cellulose.

The carbonates need not be precipitated, however. A strong base may be added to the reaction mixture to dissolve the hydroxyethyl cellulose. Any strong base, or ganic or inorganic, may be used. Among those that may be so used are tetramethylammonium hydroxide, sodium hydroxide, tetraethyla'mmo'nium hydroxide, potassium hydroxide, etc.

The particular method and reactant used will depend on the use to 'which the hydroxyethyl cellulose is to be put. I

Reaction mixtures preserved by the method of this invention have at least as good protectionagainst viscosity drop due to oxidative degradation as could be obtained in either of the processes known to the prior art. As compared with the dilution process of the prior art, the instant process affords considerably better protection against viscosity drop due to oxidative degradation. In addition, the product of this invention is easier to handle, costs less to ship, and is easier to store for extended periods (i. e., need not be hermetically sealed and kept in the dark) than is the product of the watering process of the prior art. Compared to the prior art acidification method, the process of this invention conserves hydroxyethyl cellulose, eliininates washing with methanol, andconserves alkali va ues.

- The term alkali as'used herein and in the claims is used in the strict sense to mean thehydroxides of thealkali metals. What I claim and desire to protect by Letters Patent 1. -A process for treating a reaction mixture containing a hydroxyalkyl cellulose and alkali to prevent degradation during retention for subsequent use over a reasonable .period of time and conserve alkali values which comprises passing carbon dioxide into the said reaction mixture containing hydroxyalkyl cellulose and alkali until the free alkali is substantially converted to carbonate and bicarbonate, permitting the alkali to remain in the form of carbonate and bicarbonate during such retention for subsequent use, and then regenerating the said alkali by adding a compound selected from the group consisting of the oxides and hydroxides of calcium, strontium, and

barium an d'rnixtures thereof to causticize the carbonate and bicarbonate.

' 2. A process in accordance with claim v1 wherein the hydroxyalkyl cellulose is hydroxyethyl cellulose.

fRef erence's-Cited .in the file of this patent UNITED STATES PATENTS Number 

1. A PROCESS FOR TREATING A REACTION MIXTURE CONTAINING A HYDROXYALKYL CELLULOSE AND ALKALI TO PREVENT DEGRADATION DURING RETENTION FOR SUBSEQUENT USE OVER A REASONABLE PERIOD OF TIME AND CONSERVE ALKALI VALUES WHICH COMPRISES PASSING CARBON DIOXIDE INTO THE SAID REACTION MIXTURE CONTAINING HYDROXYALKYL CELLULOSE AND ALKALI UNTIL THE FREE ALKALI IS SUBSTANTIALLY CONVERTED TO CARBONATE AND BICARBONATE, PERMITTING THE ALKALI TO REMAIN IN THE FORM OF CARBONATE AND BICARBONATE DURING SUCH RETENTION FOR SUBSEQUENT USE, AND THEN REGENERATING THE SAID ALKALI BY ADDING A COMPOUND SELECTED FROM THE GROUP CONSISTING OF THE OXIDES AND HYDROXIDES OF CALCIUM STRONTIUM, AND BARIUM AND MIXTURES THEREOF TO CAUSTICIZE THE CARBONATE AND BICARONATE. 